Process of preparing cellulosic spinning solutions and soft-luster products thereof



Patented May 25, 1937 PROCESS OF PREPARING CELLULOSIC SPINNING SOLUTIONSAND SOFT-LUS- TER PRODUCTS THEREOF Thomas H. Byron and Rudolph S. Bley,Elizabethton, Tenn., assignors to North American. Rayon Corporation, NewYork, N. Y., a corporation of Delaware No Drawing. Original applicationAugust 13,

1934, Serial No. 739,636. Divided and this application February 5, 1935,Serial No. 5,148

11 Claims. (01. 10640) This application is a division of Process ofpreparing cellulosic spinning solutions and softluster products thereof,Ser. No. 739,636, filed August 13, 1934, by Thomas H. Byron and RudolphS. Bley.

The present invention relates to a process of producing cellulosicspinning solutions and softluster products thereof of pleasing hand.

A short while after rayon yarns became durable and uniform enough tocreate a popular demand, it became evident that the high luster offabrics Woven fromthem, hitherto considered an advantage, wasobjectionable in many fabric constructions. The first delustered rayonto achieve any degree of commercial success was produced by causing theformation of small air bubbles inside the individual filament. Rayondelustered with oil, possessing more strength than the'originalair-delustered yarn became immediately popular. Subsequently othermethods, for example the dispersing of pigments, such as titaniumdioxide, etc., were introduced to modify the original luster of rayonproducts.

One object of our invention has to do with the emulsion of halogenatedoils, fats, waxes and resins in cellulosic spinning solutions to form,after extrusion,.filaments of subdued luster, said filaments retainingtheir tensile strength while having a pleasing hand.

Another object of our invention relatesto the emulsification ofchlorinated oils, fats, waxes and resins with cellulosic spinningsolutions for the aforementioned purpose.

A third object of this invention relates to the incorporation ofbrominated oils, fats, waxes and resins into cellulosic spinningsolutions, such as viscose and cuprammonium cellulose to form byextrusion dull-luster products. A fourth object of our invention has todo with the dispersion of halogenated oils, fats, Waxes and resins incombination with other luster-modifying agents, such as water-insoluble,inert solvents, pigments, etc., in cellulosic spinning solutions of theaforementioned type.

Other objects of our invention will become apparent to those skilled inthe art after a study of the following specification.

We are Well aware that it has, heretofore, been proposed to producesoft-luster, cellulosic prod- 50 ucts by incorporating therein fatty andmineral oils, paraflin, Montan wax, Halowax, chlorobenzene, etc., but wehave unexpectedly found that the physical properties of such productscan be increased by replacing the aforementioned substances withhalogenated oils, fats, Waxes, and

resins. In addition, due to the fact that the halogenation of suchsubstances results in denser compounds, it is possible to producesoft-luster products with relatively small amounts of delusteringagents. In addition, the incorporation of our halogenated delusteringagents not only improves the tensile strengths of soft-luster,cellulosic products in comparison to those heretofore attained, but itmakes the production thereof more economical.

The halogenation of oils, fats, waxes and resins can be carried out withany of the well known methods.

The substances to be halogenated may, for example, be first dissolved incarbon tetrachloride and subsequently chlorine or bromine in gaseousform introduced therein until the heat of reaction abates. Halogenatedcompounds, containing about 25 to 40% of chlorine or bromine may beobtained in this manner. However, if the introduction of halogens isprolonged, solid and translucent bodies may be obtained containing up toabout 75% of chlorine or bromine. It is to be noted in this connectionthat the fusing or boiling points of the raw materials are eitherlowered or raised by halogenation. When colophony, for

example, is dissolved in carbon tetrachloride and chlorine introducedtherein until the mixture has cooled down to room temperature, the finalproduct contains about of chlorine and it has a fusing point of about 94C. If more chlorine is introduced at room temperature, reaction productscontaining about 60% of chlorine may be formed having a fusing point ofabout 115 C. Paraffin, treated in this manner, results in productscontaining about 70% of chlorine, these products being able to resistattack by boiling nitric acid or strong caustic soda. Hydrochloric orhydrobromic acid, formed during the reaction, must be removed,preferably by neutralization. Catalysts, such as iron, etc., may beadded to the mixture to accelerate halogenation. Halogenation Will alsoproceed more rapidly by carrying out the reaction under exposure toultra-violet rays.

The halogenation of oils, fats, waxes, and resins may also be performedin accordance with methods disclosed in U. S. Patent No. 989,225 toBlakeman of April 11, 1911; No. 1,191,916 to Brooks of July 18, 1916;No. 1,246,810 to Ellis of November 13, 1917; No. 1,432,761 to Koch ofOctober 24, 1922; etc.

The halogenated substances may be emulsified in conventional viscose andcuprammonium cellulose solutions With or without the assistance ofsuitable emulsifying agents, such as soaps, ethylene, glycols, etc. Theymay also be dissolved in inert, volatile organic solvents and theresulting composition emulsified with the spinning solutions. Pigments,for example titanium dioxide, may be dispersed in dissolving or moltenhalogenated substances and these mixtures uniformly distributed in theviscose or cuprammonium cellulose solutions to modify the luster of thefinished products.

Example 1 About 1 to 10% of a halogenated oil, fat, wax or resin isemulsified in a conventional viscose solution, these percentages beingbased upon the cellulose content of the aforementioned solution. Afterextrusion into conventional spinning baths, more or less delusteredfilaments, ribbons, films, etc. of viscose may be obtained. If thehalogenated substance selected is diflicultly emulsifiable in thespinning solution, a proper distribution of its globules may be broughtabout with the assistance of suitable emulsifying agents, or it mayfirst be dissolved in an inert, water-insoluble hydrocarbon and the'liketo form a composition which subsequently is emulsified with the viscosesolution. A variation of this process consists in fusing a solid,halogenated substance, for example chlorinated paraffin, anddistributing a finely ground pigment therein. The still liquid mixtureis then emulsified with the spinning solution. Such highly chlorinatedor brominated parafiins are especially suitable for diminishing theluster of viscose products. However, we wish to emphasize that ourinvention is not limited to the use of chlorinated or brominatedparaffin. The following table depicts a number of substances which,after halogenation, become improved delustering agents for rayon:Oils.O1ive oil, cottonseed oil, Chinese-wood oil, linseed oil, castoroil, hemp oil, poppy oil, soya bean oil, pumpkin oil, bone oil, paraffinoil, mineral oils, asphalt oils, machine oil, essential oils such asturpentine, pine oil, etc.

Fats.Lard, lanoline, beef tallow, suet, etc.

Waxes. Carnauba wax, candelilla wax, bees wax, insect wax, cetaceum',ozocerite, solid parafiin, neftigil, ceresin, Vaseline, Montan wax, etc.

Resins-Resin, condensation resins, etc.

From the above it will be seen that we can use vegetable, animal andmineral oils, vegetable and animal fats, vegetable, animal and mineralwaxes, and natural and synthetic resins, which produce,afterhalogenation, improved agents for delustering cellulosic products.

Example 2 Instead of incorporating the aforementioned, halogenatedsubstances into viscose spinning solutions, they are emulsified withcuprammonium cellulose solutions. The percentages and compoundsenumerated in Example 1 may be used in connection'with cuprammoniumcellulose to form soft-luster products therefrom.

We wish to point out that the above examples are merely illustrative,and we do not wish to be limited to the exact proportions, set forthabove, which are typical combinations, as certain of these compounds maybe omitted or replaced by others of similar nature, and the proportionswithin wide limits may be varied. In other words, while we have foundthat the halogenated compounds above mentioned give the desired results,We do not wish to be limited to the use of all of these compounds, tothese compounds an H Qthers,

nor to the exact proportions and concentrations, set forth above, as aconsiderable Variation of proportions will not adversely affect thefinal products, although it may vary somewhat the relativecharacteristics of such products, resulting from such variations.Modifications will manifest themselves to those skilled in the artwithout departing from the spirit and scope of our invention, as definedby the appended claims.

We wish to emphasize, however, that only such halogenated compounds arecontemplated which are stable in alkaline and acid solutions whilebeing. substantially insoluble therein, that the term cellulosicsolutions is limited to viscose and cuprammonium cellulose solutions,that the term halogenated substances embraces only chlorinated andbrominated compounds and not iodinated and fiuorinated ones, that theterm waxes does not include aromatic compounds, such as halogenatednaphthalenes, etc., sold under the. trade-name Halowax, and that theappended claims should be read with these limitations.

We claim:

1. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solu tion selected from the group consisting ofviscose and cuprammonium cellulose together with a sufficient amount ofa compound selected from the group consisting of chlorinated andbrominated essential oils to diminish the luster of the products spunfrom said solution.

2. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from the group consisting ofviscose and cuprammonium cellulose and a sufficient amount of achlorinated pine oil to diminish the luster of the products spun fromsaid solution.

3, A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from the group consisting ofviscose and cuprammonium cellulose and a sufficient amount of abrominated pine oil to diminish the luster of the products spun fromsaidsolution.

4. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from the group consisting ofviscose and cuprammonium cellulose and about 1 to of a substanceselected from the group consisting of chlorinated and brominatedessential oils, said percentages being based upon the cellulose contentof the solution.

5. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from the group consisting ofviscose and cuprammonium cellulose and about 1 to 10% of a chlorinatedpine oil, said percentages being based upon the cellulose content of thesolution.

6. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from thegroup consisting ofviscose and cuprammonium cellulose and about 1 to 10% of a brominatedpine oil, said percentages being based upon the cellulose content of thesolution.

'7. A soft-luster cellulosic product selected from the group consistingof viscose and cuprammonium cellulose containing a small amount of acompound selected from the group consisting of chlorinated andbrominated essential oils in a sufficient amount to diminish the lusterthereof.

8. A soft-luster cellulosic product selected from the group consistingof viscose and cuprammonium cellulose containing a small amount of achlorinated pine oil in a sufficient amount to diminish the lusterthereof.

9. A soft-luster cellulosic product selected from the group consistingof viscose and cupramimonium cellulose containing a small amount of abrominated pine oil in a sufficient amount to diminish the lusterthereof.

10. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from the group consisting ofviscose and cuprammonium cellulose together with a sufiicient amount ofa chlorinated turpentine to diminish the luster of the products spunfrom said solution.

11. A spinning solution for the manufacture of soft-luster productscomprising a cellulosic solution selected from the group consisting ofviscose and cuprammonium cellulose together with about 1 to 10% of achlorinated turpentine, said percentages being based upon the cellulosecontent of said solution.

